Method for making colored crepe paper with insoluble dyes and resulting product



. Aug. 16. 19 6 F2. ALDEN fi METHOD FOR MAKING COLORED CREPE PAPER WITH INSGLUBLE DYES AND RESULTING PRODUCT Original Filed Nov. 12, 193

Patented Aug. 16, 1932 UNITED STATES PATEN OFFICE KANUFACTURING COMPANY, OF MASSACHUSETTS 0F FBAMINGHAM, MASSACHUSETTS, A CORPORATION IEI'HOD FOR MAKING, COLORED CREPE PAPER WITH INSOLUBLE DYES AND RESOLTING PRODUCT r 'origlnal application mea xovember 12, 1926, Serial m. 147,959. Divided and this application filed April 2, 1930. Serial No. 441,140.

This invention relates to a method for'the' manufacture of non-bleeding colored crepe paper and to the resulting product.

It has been proposed and described in a copending application of Galen H. Sayler (Serial No. 139,176 filed sued as Patent 1,7 32,540, dated October 22, 1929, to produce colored crepe paper by treat ing a sheet of suitable paper with a dye solution and with a fixing solution, successively or simultaneously, and then creping the thus dyed sheet as by passing it through the usual creping bath and over acreping roll. In this course of procedure there arecertain limitations and disadvantages which may arise in the course of practical operations which it is desirable to overcome or avoid. For example,

in such processes some fixing reagents, such as aluminum sulfate or the like, cause the precipitation of the adhesive (which lt ls often desirable to provide in the creping bath),

thus destroying it for further use. Moreover, the adhesive and some fixing agents or dyes tend to accumulate upon the creping roll and interfere with the proper creping operation,

or lines in the paper, and

forming streaks thus finally necessitate a thorough cleaning of this part of the machine. This is especiallylikely to occur when the creping roll is heated. Again, certain reagents" (such as tannic acid and inorganic salts) may react with and corrode the surface of the iron creping roll. This makes and regrind the roll to obtain a true cylindrical surface, involving a prolonged and difficult operation requiring a considerable amount of time and special equipment. On the other hand, acid resistant alloys would be extremely expensive,'even if it were possible to provide them in sufliciently large slzes.

Accordingly, it is an object of the present invention to provide an improved method for making colored crepe paper, whereby such disadvantages and difiiculties, when they occur, may be avoidedand to produce a satis- Other objects factory non-bleeding colored crepe paper. will appear from the disclosure and claims. o

v The method of the invention includes gen- October 2, 1926) is it necessary to removequired.

erally the treatment of asheet of paper with the dye solution or the fixing agent or such other reagent materials as may not deleteriouslyafl'ect the creping bath or creping oper- 'ation, then creping the sheet, and subsequently applying to the creped sheet such active reagent materials as may be required and in such a manner as substantially to preserve the crepedstructure of the sheet.

For example, a sheet of paper may be first treated with a dye solution inert with respect to the creping bath and creping. apparatus, then creped (with or without the use ofadhesive) and the dyed and creped sheet then treated with the appropriate fixing or other reagents. In such cases the dye solution may serve also as a creping bath and,if desired, a suitable adhesive may be added thereto or a separate creping bath may be employed.

A further improvement in the method may be effected by dissolving the fixing reagent (especiall when applied after the creping operation in such a solvent or in such concentration that it does not seriously affect or reduce the crepe of the sheet. On the other hand, the paper may first be treated with the fixing reagent (where the fixing reagent may be added to or contacted with the creping bath without detriment) and the paper then creped, and the creped paper subsequently treated with an appropriate dye solution.

A specific and'representative instance of the application of the invention will now be described as carried out by means of the apparatus illustrated in the accompanying drawing in which The figure is a' diagrammatic side eleva tion of the several pieces of apparatus re- Re'ferring to the drawing, numeral 1 indicates a roll of the paper to be treated, which is carried upon a roller 2 rotatably mounted at 3. The creping apparatus 4 includes a guide roller 5, a floodlng bar 6, a rubber roller 7, which dips into the; solution 8 con 7 and in pres tained in tank 9. Above roller sure contact therewith is provided a creping roll 10 rotatably mounted and having a doctor blade 11 in close contact with its peripheral surface at the desire ofi-take point of as desired. suitable drying apparatus, if necessary, and

solution or fixing reagent) comprises a flooding bar or roller 13, a pair of compression rollers, including a lower roller 14 (which may have a felted or other resilient and/or irregular surface), dipping into the solution 15 in tank 16, and an upper roller 17 which may or may not apply a treating solution This apparatus is followed by a rewinder or other gathering apparatus, not shown.

Appropriate dye solutions for use in the operation of the method may be prepared as follows:

1. For red:

Erie fast scarlet 4 BA (Color Index #326-Schultz #279) 5 lbs. Water gallons 2. For orange:

P-heno orange 0 (Color Index #621-- Schultz #11) 5 lbs. Water 60 gallons 3. For orange:

Aux-amine (concentrated) (Color Index 655Schultz #493) 32 ounces Rhodnmine 6 GUN ex (Color Index #752- Schultz #571, a xanthine basic dye) 14 ounces Water 60 gallons 4. For green:

Auramine (concentrated) (Color Index #655Schultz {493} 60 ounces Methylene blue Color Index #922- Schultz #659) 80 ounces Water 60 gallons The adhesive used for facilitating and 1mpzovmg the creping operation (if any) may". glue, dextrine or the like and may be disor in the fixing reagent solved in the dye employed indesolution or, as noted above, pendently.

An active fixing agent .(as for the dye solution 1 and 2 above mentioned) may con sist, for example, of an aqueous solution of aluminum sulfate. Owing to the wettin and de-crepin effect of water, it is desirab e, as later exp tionwhenever it is applied to paper which has been previously creped. To this end a concentrated solution of ammonium sulfate may be added thereto. Thus, a solution containing both-15 lbs. aluminum sulfate, 180 lbs. ammonium sulfate, 60 galsof waterhas been found well suited for the purpose. The two salts may, however, be contained in separate solutions, the concentrated am monium sulfate solution being applied in the form of a spray, for example, and the aluminum sulfate solution (preferably though-not necessarily concentrated) by means of the roller 14 or other device. The presence of the second salt ma serve function of fireproo ng the sheet.

Preliminary to the operation of the appa ratus, the sheet 1 is drawn from roller 2 and passed over guide roller 5, beneath flooding bar 6 and over roller 7 between roller 7 and ained, to use a concentrated soluthe additional.

creping roll 10, over the surface of the creping roll to the doctor blade 11, from which it is carried under flooding bar or roller 13 and between the felted rollers 14, 17 and thence to the drying and take-up mechanism. The sheet may be drawn through the apparatus, but since this tends to stretch and remove the crepe efiect, it is preferable to positively drive the several rollers in unison with each other, in the directions indicated by the arrows.

With the apparatus thus arranged, the dye solution,for example, such as that indicated by the first formula above given, is run into the tank 9, together with the adhesive if such is to be used. As already pointed out the dye solution may be separately applied to the sheet first and the sheet then passed through a creping solution in tank 9, but unless intermediate drying is'resorted to, the dye and glue should be mutually inert in this order of procedure. .The fixing solution (given above) is then placed in tank 16, or the alum solution only, and means provided (not shown) for spraying the ammonium sulfate solution upon the top of the sheet or upon roller 17.

The sheet of paper is now passed by rota tion of the several rollers under a pool of the dye solution, which is carried upon its upper surface in the depression formed-by thefiooding bar 6, and distributed throughout the width of the sheet by the transverse contact of the bar. As the sheet proceeds andcomes ino contact with the surface of roller 7 (which is wet with the dye solution) it is wet upon its under surface, and as the sheet continues to pass between roller 7 and creping roll 10 it is. firmly compressed and squeezed.

of the solution throughout the sheet, both laterally and transversely through the sheet, but effectively expresses the surplus of the dye solution which thereupon passes through the sheet and flows down upon its upper surface and maintains the 001 of dye solution adjacent to the flooding ar. The sheet is also thereby brought into intimate contact with the creping roll to which it firmly adheres until it reaches the doctor blade 11 which skives the sheet from the surface of the roll. In this removal of the .sheet from the creping roll, the paper is repeatedly folded back upon itself, forming a succession of wrinkles therein. The size of the folds thus produced depends partly upon the angle at which the doctor blade is set with respect to the surface of the creping roll and upon the shape of doctor blade and is also governed by the degree of adhesion of the sheet to the roll surface. In general, the more firmly the sheet adheres to the roll, the more numerous and closely packed the folds of the crepe may be made, and the finer the oreping produced. It is also possible to provide and pre- This not only completes the uni-- form distribution which is especially desirable.

serve a high crepe ratio by this Bprocedure y crepe ratio is meant the proportion which a given length of the sheet bears to the length of the cre ed sheet resulting therefrom.

he creped sheet may be removed at this point and dried, if desired, and the subsequent treatment independently conducted at a later time, or it may pass directly and continuously to such treatment. In either case, the creped sheet, already colored is next subjected to the fixing treatment. For example,

the sheet of crepe paper is passed under a pool of the solution held by flooding bar 13 and thence between the rollers 14 and 17. The lower roller dips into the bath of reagent 15 1s thoroughly wet thereby and carries the solution up and applies it to the'under surface of the creped sheet as it comes into contact therewith and distributes it more uniformly thereover as the paper passes under compres-' sion between the rolls.

While the wetting of crepe paper stock with water or dilute aqueous solutions always reduces the crepe ratio to a considerable extent or almost entirely destroys the creped structure, it is found that with concentrated .solutions of certain inorganic electrolytes (for example, salts such as ammonium sulfate, sodium nitrate, sodium chloride, sodium sulfate, which are substantially neutral with respect to paper, to prevent deterioration of the sheet) this effect is practically negligible.v

Again, organic solvents have little or no destructive effect upon crepe paper and some organic liquids, such as alcohol, may contain as much as 50% of water and still remain ineffective toward the creped structure of a paper sheets Accordingly, in any specific instance it is practicable to impart an initial crepe ratio to the paper of such an order that even though a part may be lost by the subsequent treatments indicated, there will be left a sufiiciently high degree of creping in the finished sheet to be entirely satisfactory for the desired purpose.

Accordingly, to this end, the amount of fixing reagent solution applied to the sheet is' kept low and a relatively high concentration of neutral salt is desirable. With such procedure, the crepe of the sheet is not destroyed, nor is it seriously afiected, although the solu tion penetrates the sheet and fixes the dye within the paper fibers, thereby rendering it substantially protected from and relatively insoluble or non-bleeding toward subsequent wetting or other forms of moisture which may come into contact with the sheet.

Moreover, if certain inorganic salts are added to or with the fixing reagent, thereby increasing the effective concentration (suchas ammonium sulfatein the example cited), the paper is simultaneously rendered slowburning or fireproof which is an obvious advantage and secured incidentally to the required operations of dyeingand fixing.

In other cases it may be advantageous, for the purpose of preserving the crepe, as above pointed out, to dissolve the reagent to be applied to the sheet in an organic solvent, which does not soften the paper or cause it to stretch under tension as does water. To this end the reagent (for example, katanol-O which is the reaction product of orthochlorophenol and sulfur in alkaiine solution) may bedissolved in alcohol, for example, and the solution thus obtained used to advantage. Again it is contemplated that the fixing reagent may be applied, per se, in an anhydrous condition, as by dissolving in a strictly .anhydrous solvent, i. e. (301. or C H Katanol (By) is a yellowish powder, soluble in hot water with addition of sodium carbonate, and possesses a direct afiinity for cotton. 10 parts of sulfur are added to a solution of 26 parts of O-chlorophenol in parts of hot Water and 8.5 parts of sodium hydroxide. The mixture is heated immediately to 100 C. under a reflux, and is boiled for 30 hours. The resinous product which separates is dissolved in 200 parts of Water and 15 parts of soda, reprecipitated with sodium sulphate, filtered and the greenish paste is dried in vacuo (Fr. Bayer & Co. E. P. 173313; cf, E. P. 22417 95, U. s. P. 603755, G. P. 102897; Guenther, Textilber, 1922, 209; cf, J. S. D. C. 1922, 38,253; Wagner, Farben-Zeit, 1922, 27, 3015).Color Index, l924-page 357.

As a modification of the application of the invention, as where the dye solution tends to corrode or accumulate upon the creping rolls, the fixing reagent may be applied to the paper first, followed by creping the paper and applying the dye solution to the treated crepe ipaperthusproduced. This'maybeeifectuated in practice by supplying the solution of fixing reagent to tank 9 and a solution of the dye to tank 16. In this order of operations, an ammoniacal solution of katanol maybe used as the fixing reagent in'conjunction with a suitable amount of adhesive (and sodium tungstate, is desired, which serves as a fire-- proofing agent). The treated sheet is then creped and-the dye solution (according to formula three or four given above) may then be applied to the creped sheet already containing the fixing reagent, with or without intermediate drying of the sheet, as required 4 nearly as readily and effectively as theaplain,

sheet before creging and the specific sequence of steps require by other methods (in which the creping' is efiected last) neednot be adhered to. This results in greater flexibility and the ready adaptation of the process to the ractical requirements of manufacture and ence facilitates control of the product and of the operation. of the method atthe several stages of procedure.-

The pro uniformity'of color'andof'crepe efie'ctand may be of'substantiallv any predetermined shade or tone de'sir'ed. The lustre of the surface, which may beenhanced by'using a paper having a {finished surface on one or both sides is, to an appreciable degree, reserved. This is especially noticeable w on an organic solvent 1s used for the fixing re.- agent. -Again,' a fine or coarse degree of creping may be imparted to the sheet as desired, and a high crepe ratio may be obtained and preserved because the subsequent treatment does not seriously impair the crepe finish. Moreover, the finished product 1s non-bleeding and the colors are relatively fast when brought into contact with moisture or even when thoroughly soaked with water." I

It is apparent that numerous modifications and adaptations of the invention may be made in its practical application and that various substitutions and combinations ofthe raw materials and reagents used may and ordinarily will berequired for specific. purposes of manufacture and use. Such modifi cations and substitutions are, however, to be considered as comprehended by theforegtiing disclosure and included within the lowing claims.

This apphcation is a division of application Serial No. 147,959, filed November 12 1926 issued as Patent 1,7 56,778, dated April 29, 1930.

I claim:

1. A method for making non-bleeding colored crepe paper, which comprises treating a sheet of paperwith a solution of a fixingv reagent, creping the treated sheet and thereafter applying a solution of dye to the creped sheet.

2. A' method for making non-bleeding colored crepe paper,-which comprises treating a sheet of paper with a solution of a fixing reagent and a fireproofing reagent, creping the treated sheet and thereafter applying a solution of dye to the creped paper.

Signed by me at Framingham, Massachusetts, the 31st day of March 1930.

' GARDNER R. ALDEN.

uct isjcharacterized by having a I saturated and 

